(Table 1) Geochemistry of ODP Hole 130-807C carbonates across the K/T boundary

Paleontological, stable isotopic, trace elemental abundance, and magnetostratigraphic studies have been performed on limestones spanning the Cretaceous/Tertiary boundary transition at Ocean Drilling Program (ODP) Hole 807C. Paleontological evidence exists for considerable resedimentation, which we attribute to the fact that Hole 807C is located in a basement graben. Age estimates based on planktonic foraminiferal biostratigraphy, as well as magnetostratigraphy, indicate that sedimentation rates could have been on the order of 12-14 m/m.y. This is significantly higher than those documented in other important Deep Sea Drilling Project (DSDP) and ODP Cretaceous/Tertiary boundary sections using the same age control points (e.g., DSDP Hole 577 and ODP Hole 690B), although not as high as those documented from DSDP Hole 524. The expanded nature of this succession has resulted in the Cretaceous/Tertiary boundary d13C decrease occurring over approximately a 9-m interval. Ir analysis of these sediments do not show a single large anomaly, as has been found in other Cretaceous/Tertiary boundary sections, but trivial background levels instead. Ce data support the hypothesis that this section has been expanded by secondary sedimentological processes.

Chemical and Sr isotopic compositions of pore fluids and marine carbonates from ODP Hole 130-807A

The 87Sr/86Sr ratios and Sr concentrations in sediment and pore fluids are used to evaluate the rates of calcite recrystallization at ODP Site 807A on the Ontong Java Plateau, an 800-meter thick section of carbonate ooze and chalk. A numerical model is used to evaluate the pore fluid chemistry and Sr isotopes in an accumulating section. The deduced calcite recrystallization rate is 2% per million years (%/Myr) near the top of the section and decreases systematically in older parts of the section such that the rate is close to 0.1/age (in years). The deduced recrystallization rates have important implications for the interpretation of Ca and Mg concentration profiles in the pore fluids. The effect of calcite recrystallization on pore fluid chemistry is described by the reaction length, L, which varies by element, and depends on the concentration in pore fluid and solid. When L is small compared to the thickness of the sedimentary section, the pore fluid concentration is controlled by equilibrium or steady-state exchange with the solid phase, except within a distance L of the sediment-water interface. When L is large relative to the thickness of sediment, the pore fluid concentration is mostly controlled by the boundary conditions and diffusion. The values of L for Ca, Sr, and Mg are of order 15, 150, and 1500 meters, respectively. L_Sr is derived from isotopic data and modeling, and allows us to infer the values of L_Ca and L_Mg. The small value for L_Ca indicates that pore fluid Ca concentrations, which gradually increase down section, must be equilibrium values that are maintained by solution-precipitation exchange with calcite and do not reflect Ca sources within or below the sediment column. The pore fluid Ca measurements and measured alkalinity allow us to calculate the in situ pH in the pore fluids, which decreases from 7.6 near the sediment-water interface to 7.1+/-0.1 at 400-800 mbsf. While the calculated pH values are in agreement with some of the values measured during ODP Leg 130, most of the measurements are artifacts. The large value for L_Mg indicates that the pore fluid Mg concentrations at 807A are not controlled by calcite-fluid equilibrium but instead are determined by the changing Mg concentration of seawater during deposition, modified by aqueous diffusion in the pore fluids. We use the pore fluid Mg concentration profile at Site 807A to retrieve a global record for seawater Mg over the past 35 Myr, which shows that seawater Mg has increased rapidly over the past 10 Myr, rather than gradually over the past 60 Myr. This observation suggests that the Cenozoic rise in seawater Mg is controlled by continental weathering inputs rather than by exchange with oceanic crust. The relationship determined between reaction rate and age in silicates and carbonates is strikingly similar, which suggests that reaction affinity is not the primary determinant of silicate dissolution rates in nature.

Foraminiferal abundances and preservation in ODP Hole 130-805C

Downcore changes in various carbonate dissolution indexes are documented for Hole 805C for the last 1.2 m.y. These indexes include degree of fragmentation of planktonic foraminifers, percent sand, abundance ratio of species of contrasting solution susceptibilities (Globigerinoides sacculifer vs. Pulleniatina, Globorotalia tumida, and Globorotalia menardii), and the difference in d18O between species of contrasting solution susceptibilities (G. sacculifer vs. Pulleniatina). These preservation indexes have been combined into a single composite dissolution index that corresponds closely to the d18O record. The rate of change of the oxygen isotope signal is also important, with glacial-to-interglacial transitions corresponding to maximum preservation events and vice versa. For information on changing productivity (which is important because an increased supply of organic matter may enhance dissolution by lowering pH upon degradation), we present the abundance of coarse-fraction benthic foraminifers per gram and the ratio between two planktonic foraminiferal species, one of which is strongly associated with equatorial upwelling (Globorotalia tumida vs. Pulleniatina). Our results suggest that productivity plays a subordinate role in determining foraminifer preservation. Furthermore, our results confirm previous observations that associate enhanced preservation events with glacial periods and with glacial-to-interglacial transitions. A correlation between preservation and sedimentation rates of these carbonate-rich sediments could not be established. Notable differences are present between the responses of individual dissolution indexes, indicating that processes other than dissolution determine proxy indexes to varying degrees.

Miocene planktonic foraminifera of ODP Hole 130-806B

We document the waxing and waning of a "proto-warm pool" in the western equatorial Pacific (WEP) based on a study of multi-species planktic foraminiferal isotope ratios and census data spanning the 13.2-5.8 Ma interval at ODP Site 806. We hypothesize that the presence or absence of a proto-warm pool in the WEP, caused by the progressive tectonic constriction of the Indonesian Seaway and modulated by sea level fluctuations, created El Niño/La Niña-like alternations of hydrographic conditions across the equatorial Pacific during the late Miocene. This hypothesis is supported by the general antithetical relationship observed between carbonate productivity and preservation in the western and eastern equatorial Pacific, which we propose is caused by these alternating ocean-climate states. Warming of thermocline and surface waters, as well as a major change in planktic foraminferal assemblages record a two-step phase of proto-warm pool development ~11.6-10 Ma, which coincides with Miocene isotope events Mi5 and Mi6, and sea-level low stands. We suggest that these changes in the biota and structure of the upper water column in the WEP mark the initiation of a more modern equatorial current system, including the development of the Equatorial Undercurrent (EUC), as La Niña-like conditions became established across the tropical Pacific. This situation sustained carbonate and silica productivity in the eastern equatorial Pacific (EEP) at a time when carbonate preservation sharply declined in the Caribbean. Proto-warm pool weakening after ~10 Ma may have contributed to the nadir of a similar "carbonate crash" in the EEP. Cooling of the thermocline and increased abundances of thermocline taxa herald the decay of the proto-warm pool and higher productivity in the WEP, particularly ~ 9.0-8.8 Ma coincident with a major perturbation in tropical nannofossil assemblages. We suggest that this interval of increased productivity records El Niño-like conditions across the tropical Pacific and the initial phase of the widespread "biogenic bloom". Resurgence of a later proto-warm pool in the WEP ~6.5-6.1 Ma may have spurred renewed La Niña-like conditions, which contributed to a strong late phase of the "biogenic bloom" in the EEP.